Engineered pine nut shell derived activated carbons for improved removal of recalcitrant pharmaceuticals in urban wastewater treatment.

Novel powdered activated carbons (PACs) from pine cones and pine nut shells (PNSs) were tested for the competitive adsorption of pharmaceutical compounds (PhCs) in spiked (100 µg/L) secondary effluent and mixed liquor from an urban wastewater treatment plant. Steam activated PNS77, with hierarchical pore structure and 1463 m2/g of BET area, outperformed the commercial benchmark (WP220, mineral origin) for PhCs and dissolved organic matter (DOM) control. PNS77 attained the highest adsorption capacity and rate in synthetic and real wastewaters. Competitive adsorption isotherms revealed the detrimental effect of direct site competing DOM on PhC removal. The PhCs' adsorbability increased with their hydrophobicity, regardless of the water matrix. Kinetic data allowed inferring that indirect competition due to pore constriction/blockage appeared to occur only in mixed liquor. Adsorption isotherm data modelling for ng/L range revealed 80 % removal of carbamazepine and diclofenac would be achieved dosing 8-15 mg/L PNS77 to secondary effluent, while for mixed liquor the dose must be doubled to balance the increased competition. Hydrophilic sulfamethoxazole required a higher dose (34-44 mg/L), lower in the mixed liquor. PNS77 hierarchical pore network and basic surface chemistry minimized DOM direct site competition, requiring lower doses in practical applications for wastewater treatment.

Solar Light-Induced Methylene Blue Removal over TiO2/AC Composites and Photocatalytic Regeneration.

TiO2-containing photocatalysts, which combine TiO2 with carbon-based materials, are promising materials for wastewater treatment due to synergistic photodegradation and adsorption phenomena. In this work, TiO2/AC composites were produced by the in situ immobilization of TiO2 nanoparticles over activated carbon (AC) derived from spent coffee grains, using different TiO2/AC proportions. The TiO2/AC composites were tested as adsorbents (dark) and as photocatalysts in a combined adsorption+photocatalytic process (solar irradiation) for methylene blue (MB) removal from ultrapure water, and from a secondary effluent (SecEf) of an urban wastewater treatment plant. All the materials were characterized by XRD (X-ray powder diffraction), N2 adsorption-desorption isotherms at -196 °C, SEM (scanning electron microscopy), UV-Vis diffuse reflectance, FTIR (Fourier-transform infrared spectroscopy), TPD (temperature programmed desorption), XPS (X-ray photoelectron spectroscopy) and TGA (thermogravimetric analysis). The TiAC60 (60% C) composite presented the lowest band gap (1.84 eV), while, for TiAC29 (29% C), the value was close to that of bare TiO2 (3.18 vs. 3.17 eV). Regardless of the material, the solar irradiation improved the percentage of MB discolouration when compared to adsorption in dark conditions. In the case of simultaneous adsorption+photocatalytic assays performed in ultrapure water, TiAC29 presented the fastest MB removal. Nevertheless, both TiAC29 and TiAC60 led to excellent MB removal percentages (96.1-98.1%). UV-induced photoregeneration was a promising strategy to recover the adsorption capacity of the materials, especially for TiAC60 and AC (>95%). When the assays were performed in SecEf, all the materials promoted discolouration percentages close to those obtained in ultrapure water. The bulk water parameters revealed that TiAC60 allowed the removal of a higher amount of MB, associated with the overall improvement of the SecEf quality.

An Update on Wastewater Multi-Resistant Bacteria: Identification of Clinical Pathogens Such as Escherichia coli O25b:H4-B2-ST131-Producing CTX-M-15 ESBL and KPC-3 Carbapenemase-Producing Klebsiella oxytoca.

Wastewater treatment plants (WWTPs) are significant reservoirs of bacterial resistance. This work aims to identify the determinants of resistance produced by Gram-negative bacteria in the influent and effluent of two WWTPs in Portugal. A total of 96 wastewater samples were obtained between 2016 and 2019. The numbers of total aerobic and fecal contamination bacteria were evaluated, and genomic features were searched by polymerase chain reaction (PCR) and Next-Generation Sequencing (NGS). Enterobacteriaceae corresponded to 78.6% (n = 161) of the 205 isolates identified by 16sRNA. The most frequent isolates were Escherichia spp. (57.1%, n = 117), followed by Aeromonas spp. (16.1%, n = 33) and Klebsiella spp. (12.7%, n = 26). The remaining 29 isolates (14.1%) were distributed across 10 different genera. Among the 183 resistant genes detected, 54 isolates produced extended spectrum ß-lactamases (ESBL), of which blaCTX-M-15 was predominant (37 isolates; 68.5%). A KPC-3 carbapenemase-producing K. oxytoca was identified (n = 1), with blaKPC-3 included in a transposon Tn4401 isoform b. A higher number of virulence genes (VG) (19 genes) was found in the E. coli 5301 (O25b-ST131-B2) isolate compared with a commensal E. coli 5281 (O25b-ST410-A) (six genes). Both shared five VG [Enterobactin; Aerobactin, CFA/1 (clade α); Type1 (clade γ1); Type IV]. In conclusion, this work highlights the role of relevant clinical bacteria in WWTPs, such as KPC-3-producing K. oxytoca, and, for the first time, a CTX-M-15-producing Ochromobactrum intermedium, a human opportunistic pathogen, and a SED-1-producing Citrobacter farmeri, an uncommon CTX-M-type extended-spectrum beta-lactamase.

Assessing the applicability of a new carob waste-derived powdered activated carbon to control pharmaceutical compounds in wastewater treatment.

This paper assesses the applicability of a new carob waste-derived powdered activated carbon (PAC) obtained by steam activation for pharmaceutical compounds (PhCs) removal in urban wastewater treatment plants (WWTPs) with activated sludge (AS) secondary treatment. The new carob-derived PAC presents chemical and textural properties similar to a high-performing commercial PAC produced from vegetable source by physical activation. The adsorption isotherms of three target PhCs, carbamazepine, diclofenac and sulfamethoxazole, spiked (at around 100 µg/L) in mixed liquor (ML) and in clarified-ML from the AS-bioreactor of a WWTP show: (i) minor reduction of PAC capacity with real MLs compared to clarified MLs; (ii) the higher the PhC hydrophobicity, the higher the PAC adsorption capacity in both water matrices; (iii) hydrophobic interactions probably overweight electrostatic interactions between the PhCs and the slightly positively charged PAC in these real water matrices with background organics and inorganics. The PhC adsorption results with ML and clarified-ML are used to calibrate the IAST-based tracer model (TRM) and predict the new PAC performance when added to AS-bioreactor vs. in post-secondary treatment, at the PhC naturally-occurring trace concentrations. The modelling projections show (i) one needs higher PAC doses than those reported in the literature, particularly in post-treatment, and (ii) the benefits of PAC dosing to the bioreactor, with only a slightly higher PAC dose being needed when compared to its post-secondary dosing and minimising the capital investment.

Desulfurization of dibenzothiophene, benzothiophene, and other thiophene analogs by a newly isolated bacterium, Gordonia alkanivorans strain 1B.

A novel bacterium, Gordonia alkanivorans strain 1B, was isolated from hydrocarbon-contaminated soil. Assessment of the biodegradation of distinct organic sulfur-compounds, such as dibenzothiophene (DBT), benzothiophene (BT), DBT sulfone, and alkylated tiophenic compounds, as the sole source of sulfur was investigated. G. alkanivorans strain 1B was able to remove selectively the sulfur from DBT while keeping intact the remaining carbon-carbon structure. Orthophenyl phenol (2-hydroxybiphenyl) was the only detected metabolic product. The bacterial desulfurization activity was repressed by sulfate. G. alkanivorans strain 1B consumed 310 microM DBT after 120 h of cultivation, corresponding to a specific desulfurization rate of 1.03 micromol/(g of dry cells x h). When an equimolar mixture of DBT/BT was used as a source of sulfur in the growth medium, G. alkanivorans strain 1B assimilated both compounds in a sequential manner, with BT as the preferred source of sulfur. Only when BT concentration was decreased to a very low level was DBT utilized as the source of sulfur for bacterial growth. The specific desulfurization overall rates of BT and DBT obtained were 0.954 and 0.813 micromol/(g of dry cells x h), respectively. The newly isolated G. alkanivorans strain 1B has good potential for application in the biodesulfurization of fossil fuels.